Process for breaking petroleum emulsions



4Ig'atented Dec. 10,1935 'v UNITED 'STATES PATENT oFFi'c-E Pnocnss FonBREAKING PETBLEUM SIONS i Charles Steht, Alhambra, Calif., assigner to'Tretolite Company, Vriilcbster Groves, Mo., la.

corporation of Misso No Drawing., Alu-lie-:ationNo'vvexnber 12, 1934,.

.- v .Serial No. 752.714 -v 5 claims. (ci-19H) i This invention relatesto the `irestaient on.

. emulsions of mineral il and water.' such as petroleum emulsions, forthe purpose of separat ing the oil from the water.

'5 Petroleum emulsions are of the walter-ir'x-oil are commonly referredto las cut oil", "roily p The object of my invention is to provide .a i15 novel, inexpensive and eincient process for separating emulsions ofthe kind referred to into their component parts of oil and waterV orbrine.'

l Brley described, my process consists in subjecting a petroleumemulsion of the water-inoil type, to the action of a treating agent ordemulsifying agent of a particular composition herein'- after described,thereby causing'the emulsion to break down and separateinto itslcomponent -parts of oil and water or brine-'when the? emul` sion ispermitted to remain inv a'quiescent state after such treatment, or isvsubjected to an equivalent separatory procedure. -v

The treating agent orl demulsifying agent that I contemplate using invmyI processis; aksfuper from blown -oiis ofthe kind" which haveheretofore been used in the arts andincidentally eml ployed in thebreaking of oil field emulsions. )It

is well known that at least some of the blown oils. a5 derived fromreactive" 'fatty 'bodieS. particularlyv castor oil, and, of the kindcommercially avail` able, may be employed to break petroleum ennui-gksions. Certain ones may be in specic com'- 1 binations, such-as thatdescribedinfill;r S. Patent 40 N0. 1,929,399,130 Fl11l8,dal2l3d` October3, 1933.

Similarly,l certainoxidized'c'astor oils maybe employed in combinationwith vpetroleum sulfona'testo form demulsifying agents, as describedin'. co1

described in my co-pen'ding application for` p'atent Serial No. 752,713;filed November 12,1934. 50 It is to be noted that blown oils have. beenused in various arts prior to their use as demulsifying agents in thebreaking of crude oill emulsions. Generally, the blown oils heretoforeemployed in the demulsication of crude oil, have consisted i ofconventionally available vblown oils derived Jolla, have beenunsatisfactory.

oxidized, semi-livery blown-oils are further charsolely from castor oil,and prepared primarily'for certain industrial purposes other than thedevmuisiiication of crude oil. Originally, they were probably preparedfor use in mixing with certain petroleum oils so as to give lubricantsof 5' high specic gravity and high viscosity. In their use insuchlubricants it was necessary to .guard against gumminess. Blownoilshave also been. used asplasticizers in various plastic materials,

,particularlyartiiicial leather, and similarly to 10 their use inlubricants, gumminess in the blown oil is not desirable. Thereforaionedistinguishing characteristic of` the conventionally available blownoilsl is the substantial absence of any gumminess, gelatinization,or-semi-livery prop- 15 erty.- 1 l i I have found that aftercommercially available blown oils are oxidized still further by means ofa subsequent treatment' with air or` oxygen 4at rather elevatedtemperatures, for instances, 150 20 to 250 C.. that one obtains anapparently new i kind of blown cil, or at least a kind of -blown oilwhich has not heretofore been employedv ,inv the =breaking of oil fieldemulsions, or, in fact, for any otherv purpose. Such:super-'oxidizedblown oils 25 are characterized by a semi-livery consistency.Furthermoregtheir conversion into a salt of the` kind described in theaforementioned Fuchs patl ,-'tent renders them substantiallyj worthlessfor 30 oxidized, semi-livery blown oil,'as distinguished( breakingoiineia emuisions.- suon b1own ons are so preferably employedwithoutneutralization, or if` i neutralized, the -neutralization must `beeffected Vvwith .aweak base, 'such as triethanolamine, so

ythat ther-eis nosaponication of anyester o'r "festerlike compoundsvthat in'ay be; present. 35 vfl'lprere is noobjectionftovtheneutralization '(sapninoiitiom 1 of neo) acids. v.If have round thisparticular type, of super-oxldized-semi-livery 4blown .oil to `beeifective on a wide variety of .i

emulsions,v :particularly certain lemulsions occur- .40

" ring in the-Los Angeles basin in California. In

treatmentv of such emulsions, thereare instances A -wh'ere other'wellknown demulsifying agents, in-

l pending application for. patent of DeGroote-a'nd f Wirtel, Serial No.'715,773,1lled March 15, 1934',i

Blown oils of the kindcommerciallyavailable may also be employed inyspecial mixtures of the kind.v

cluding ordinary conventionally available blown These super- 45acterized bythe fact *that slight additional oxidation renders themkerosene-insoluble. Theyi i do not appear to be suitable for thepurposes forv Awhich ordinary conventionally available blown oilsareintended. i. e., foruse in lubricants or as lpla'stlcizers in artificialleather;

In order to clearly emphasize the fact that the blown voils Icontemplate using are produced, by

y, prolonged or more drastic oxidation than is Aemployed in theproduction of ordinary blown oils, I will refer to the blown oilscontemplated by my process as super-oxidized blown oils, and in order todistinguish them from ordinary blown oils which are free from anygumminess or gelatinization, I shall refer to them as semi-livery blownoils. It should be understood, however', that the words semi-liveryrefer to these blown oils as freshly prepared, because any oil capableof oxidation or polymerization, if allowed to stand long enough, mayultimately become semi-livery, or even solid, in some instances. Inother words, the blown oils used as the demulsifying agent of my processare semi-livery when freshly prepared. Semi-livery, super-oxidized blownoil of the kind above referred to can be prepared by first continuingoxidation of commercially blown oils until kerosene-insolubility isreached, and then repeating the process a second time on a new sample,but with caution that the second time oxidation should stop at a pointjust short of kerosene-insolubility. In order to indicate the point atwhich super-oxidation must cease, I have herein referred to such oils asbeing super-oxidized just short of kerosene-insolubility. Thisparticular characteristic clearly denes these oils as being oxidizedbeyond ordinary conventionally available blown oils, but not oxidizedquite enough to give kerosene-insolubility. At this particular pointthese blown oils possess the gummy, semilivery physical characteristicpreviously referred to.

I may use these blown oils as such o`r after neutralization withtriethanolamine, or after mixture with any suitable solvent of the kind'well known in the art for admixture with crude oil demulsifying agents.The solvents most frequently used include conventional petroleumdistillates, such as kerosene, gasoline, stove oil, etc.; coal tardistillates, such as benzol, solvent naphtha, etc.; alcohols, suchasethyl alcohol, methyl alcohol, denatured alcohol and also isopropylalcohols, such as butyl alcohol, propyl alcohol, etc. The solvent orsolvents selected'will depend in part on the reactive fatty bodies usedas raw materials in preparing the specific blown oils employed as thedemulsifying agents of my process. As previously stated, these productsmay be neutralized to the extent that any free acidic hydrogen may beneutralized with a base, provided that the base does not saponify orbreak down any esters or ester-like compounds. I have not found causticsoda to be a suitable base, but have found triethanolamine to beparticularly adaptable for neutralization.

I may use the above described drastically oxidized, semi-livery blownoil or oils alone or in combination with one or more other well knowndemulsifying agents. I particularly prefer to use such oil in a mixtureof the kind described in my co-pendingV application' for patent SerialNo. l752,713, filed November 12, .1934, above referred to.

Such super-oxidized blown oils may be preparedfrom blown castor oil orblown oil derived from some other suitable oils, such as corn oil,sesame oil, cotton seed oil, rape seed oil, or a mixture of one or moreof these oils with castor oil. It is obvious that the production ofthese super-oxidized blown oils need not be a twostep process, butinstead, one may start. with an unoxidized fatty body and simplycontinue the oxidation in one continuous step until products of thedesired characteristics are produced. Similarly, instead of employingthe oils themselves,

such as castor oil, corn oil, cotton seed oil and the like, or mixturesof thesame, one may employ the fatty acids thereof or mixtures of thesame, or mixtures of the fatty acids and the naturally-oc'- curringglycerides. Accordingly, I Wish it to be understood that the expressionAsuper-oxidized blown oils is not intended to be restricted to the blownglycerides alone, but may' apply equally'well to blown fatty acidscorresponding to the' glycerides or to a mixture of the same withglycerides.

The treating agent or demulsifying agent that I prefer to use in myprocess is prepared in the following manner: Iremploy as a raw materialany non-gummy blown castor oil, free from semi-livery characteristicsand of thetype conventionally employed in the manufacture of lubricantslor used as a plasticizer in articial leather; I heat a small quantity ofthis oil to approximately 200 C. and then subject it to violentagitation with a current of air until samples taken at short intervalsreveal 'a semi-livery 4consistency and in,- solubility to kerosene. Irepeat this procedure on' a large scale but employ a slightly lower`temperature and a slightly shorter period of oxidation so as to reach apoint just short' of keroseneinsolubility, previously referred to, butcharacterized by a semi-livery structure. I nd that this particularreagent or product is perfectly satisfactory for use as a demulsifyingagent or ltreating agent in the demulsilcation of crude oil emulsions,and will break many emulsions not susceptible' to treatment with theconventionally available blown oils, and in certain instances, notsusceptible to treatment with other available semi-drying oils. For thesake of convenience, I dilute this super-oxidized, semi-livery' blownoil while still warm (60 to '70' C.), with an equal volume of kerosene,and for the treatment of some emulsions I add a smallamount oftriethanolamine so as to neutralize any free carboxylic hydrogen withoutdecomposing any esters or esterlike combinations or similar bodies whichmay be present. v l Y Y The superiority of the treating orA demulsifyingagent contemplated by my process is based upon its ability to treatcertainemulsions moreadvantageously and at a somewhat lower cost than ispossible with other known demulsiers, or conventional mixtures thereof.It is believed that the particular demulsifying agent or treating agentherein described will find comparatively limited application, so far asthe majority of oil eld emulsions are concerned; but I have found thatsuch a demulsifying agent Vhas commercial value, as it will economicallybreak or resolve oil eld emulsions in .a certain number of lcases whichcannot be treated as easily andat so low a cost with the demulsifyingagents heretofore available.l

In practising my process, a treating agent or demulsifying agent of thekind described above may be brought in contact with the emulsionto betreated in any of the numerous ways now employed in the treatment ofpetroleum emulsions of the water-in-oil type with chemical demulsifyingagents, such, for example, as by introducing the treating agent intothe-well in which the emulsion is produced; introducing the treatingagent into a conduit through which the emulsion 70 oil storage tank. Insome instances, ,it may be 75 acaaovo advisable to introduce thetreating agent into a producing well in such a way that it will becomemixed with water and oil that are emerging from the surrounding strata,before said'water and oil enter the barrel of the well pump or thetubing up through which said water and oil flow to the surface of theground. After treatment, the' emulsion is allowed to stand in aquiescent state,l

usually in a settling tank, and usually at a temperature varying fromatmospheric temperature to about 200 F., so as to permit the water orbrine to separate from the oil, it being preferable to keep thetemperature low enough to prevent the volatilization of valuableconstituents of the oil. If desired, the treated emulsion may be actedupon by one or more of the various kinds of apceptionally refractoryemulsions of the -kindsv known as tank bottoms and residual pit oils,the ratio of 1:500 above referred to, may be required. In treating freshemulsion, i. e., emulsions that will yield readily to the action ofchemical demulsifying agents, the ratio of 1:30,000, above referred to,maybe sufficient to produce highly satisfactory results. In general, Ihave found that for an average petroleum emulsion a ratio of 1 part oftreating agent to 5,000 parts of emulsion will usually be found toproduce commercially satisfactory results.

Having thus described my invention, what I claim as new and desire tosecure by Letters Patent is:

1. A process for breaking petroleum emulsions of the water-in-oil type,which consists Yin subjecting the emulsions to the action of ademulsifying agent produced or derived by the super-oxidation of acastor oil body in which oxidation has been continued until thesuper-oxidized mass is semi-livery in consistency when freshly prepared,

-is semi-livery in consistency when freshly preand isffurthercharacterized by the fact that oxidation has been carried to a pointjust short of kerosene-insolubility.

2. A process for breaking petroleum emulsions ofthe water-in-oil typ.which consists in sub- 5 jecting the emulsions to the action of ademulsifying agent produced or derived by the superoxidation of a castoroil body in which oxidation has been continued until the super-oxidizedmass 10 pared and is further characterized by the fact lthatoxidationha's been carried to a point just short ofkerosene-insolubility, followed by dilution with a suitable solvent. y

3. A process for breaking petroleum emulsions 15 of the water-in-oiltype, which consists in subjecting the emulsions to the action oiE ademulsifying agent produced or derived by the superoxidation of a castoroil body in which oxidation vhas been continued until the'super-oxidized mass 20A is semi-livery in consistency when freshlyprepared and is further characterized by the fact that oxidation hasbeen carried to a point just short of kerosene-insolubility, followed bydilution with kerosene. 25 4. A process for breaking petroleum emulsionsof the water-in-oil type, which consists in subjecting the emulsions tothe action of a demulsifying agent produced or derived by thesuperoxidation of a-castor oil body in which oxidation 30 has beencontinued until the super-oxidized mass is semi-livery in consistencywhen freshly prepared and is further characterized by the fact thatoxidation has .been carried to a point just short ofkerosene-insolubility, followed 'by dilution with an equal volume ofkerosene.

5. A process for breaking petroleum emulsions of the water-in-oil type,which consists in subjecting the emulsions to the action of ademulsifying agent produced or yderived by the superoxidation of acastor oil body in which oxidation has been continued until thesuper-oxidized mass is semi-livery'in consistency when freshly pre,-pared and is further characterized by the fact that oxidation has beencarried to a point just 45 short of kerosene-insolubility, followed bydilution with an equal volume of kerosene and subsequent neutralizationof all the acidic hydrogen by means of triethanolamine. v

' CHARLES N. STEHR.

